Efficient oil–water separation plays a vital role in treating large amounts of industrial wastewater. However, current traditional separation methods are entwined with problems such as low efficiency and poor operability. Herein, we reported a nanofiber based on electrospinning and electrospray technology and spraying microspheres on the surface of a fiber mat for efficient oil–water separation. Owing to the electrostatic repulsion among the microspheres, the surface of the developed membrane had a honeycomb-like through-hole structure and super-high oil–water separation efficiency and oil flux. After 10 cycles, the membrane showed good separation efficiency and flux. This innovative work may provide a new idea and method for the design of biomimetic biopolymers, with broad application prospects in the field of oil–water separation.